final project report1 compressed

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A Project Report

On

Designing And Kinetic Modelling Of Slurry Based Photo

Catalytic Reactor

(B.E. Environmental Science and Engineering)

Submitted By

Dhruv Bhatt (120570137001)

Abhijit Dave (120570137051)

GTU Team ID: 44239

Under the Guidance of

Prof. Varun Agarwal

(Assistant Professor)

To be carried out at

Department of Environmental Science and Engineering

Faculty of Engineering

Affiliated to

Gujarat Technological University

2015-2016

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Marwadi Education Foundation’s Group of Institutions

Rajkot-Morbi Highway,

Near Gauridad, Rajkot,

Gujarat-360003

DECLARATION

We hereby declare that the Project Report for the project entitled “DESIGNING AND

KINETIC MODELLING OF SLURRY BASED PHOTO CATALYTIC REACTOR”

submitted in fulfilment for the degree of Bachelor of Engineering in Environmental Science

and Engineering to Gujarat Technological University, Ahmedabad, is a Bonafide record of

the project work carried out at Marwadi Education Foundation’s Group of Institutions under

the supervision of Prof. Varun Agarwal (Assistant Professor) and that no part of any of the

reports has been directly copied from any student’s reports or taken from any other source,

without providing due reference.

Name of the Students Signature of Students

Dhruv Bhatt

Abhijit Dave

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Gujarat-360003

CERTIFICATE

This is to certify that the project report, submitted along with the project entitled

“DESIGNING AND KINETIC MODELLING OF SLURRY BASED PHOTO

CATALYTIC REACTOR” has been carried out by Dhruv Bhatt, under my guidance in

fulfilment for the degree of Bachelor of Engineering in Environmental Science and

Engineering (8thSemester) of Gujarat Technological University, Ahmadabad during the

academic year 2015-16. This student has successfully completed project activity under my

guidance.

Internal Guide Head of the Department

Prof. Varun Agarwal Prof. Ashish Gulabani

(Assistant Professor) (Head of the Department)

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Gujarat-360003

CERTIFICATE

This is to certify that the project report, submitted along with the project entitled

“DESIGNING AND KINETIC MODELLING OF SLURRY BASED PHOTO

CATALYTIC REACTOR” has been carried out by Dhruv Bhatt and Abhijit Dave, under

my guidance in fulfilment for the degree of Bachelor of Engineering in Environmental

Science and Engineering (8thSemester) of Gujarat Technological University, Ahmadabad

during the academic year 2015-16. These students have successfully completed project

activity under my guidance.

Internal Guide Head of the Department

Prof. Varun Agarwal Prof. Ashish Gulabani

(Assistant Professor) (Head of the Department)

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ACKNOWLEDGEMENT

After completing four years of my degree, I stand on the verge of graduation and an

important part of life. To achieve this feat was no easy accomplishment and it could only be

done with the help, support and contribution of many.

I would like to express a deep sense of gratitude and thank to Prof. Ashish Gulabani, Head

of the Department, Dept. of Environmental Science and Engineering, MEFGI for allowing us

to embark on this project.

I extend my sincere thanks to my guide Prof. Varun Agarwal, Dept. of Environmental

Science and Engineering, MEFGI under whose guidance, support and advice has made it

possible to successfully complete our project.

I am also thankful to all the faculty of Environmental Science and Engineering Dept. and the

reviewers for their numerous suggestions.

Finally, special thanks to parents and friends for they stood by me at all times patiently with

their love, understanding and affection.

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ABSTRACT

The textile units use a number of dyes, chemicals and other materials to impart desired

quality to the fabrics. These units generate a substantial quantity of effluents, the quality of

which in most of the cases are unsuitable for further use and can cause environmental

problems, if disposed off without proper treatment.

The conventional treatment processes have various disadvantages and limitations, therefore,

cannot be successfully implemented in the textile industry. Advanced oxidation processes

seem to be promising as these methods can efficiently degrade the highly toxic and

recalcitrant compounds and do not generate any secondary pollutants for disposal.

This Report seeks to give an overview of the different advanced oxidation methods for

treatment of textile industry effluents. In this report, introduction of photo catalysis process,

designing of photo reactor and results of experiments have been discussed.

Maximum degradation of 83-84% was found on natural pH of sample dye of 200 ppm

concentration and at 2 g/L concentration of TiO2.

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Table of Contents LIST OF TABLES………………………………………………………………………….……………..….9

LIST OF FIGURES………………………………………………………………………….…….…..….…10

ACRONYMS................................................................................ ...................................................................11

CHAPTER 1 .............................................................................................................................................12-16

1 INTRODUCTION ................................................................................................................................12-16

1.1 INTRODUCTION OF ADVANCED OXIDATION PROCESS.............................................................12

1.2 THEORY OF ADVANCED OXIDATION PROCESS…………………………………….…….....12-13

1.3 CLASSIFICATION OF ADVANCED OXIDATION PROCESSES......................................................13

1.3.1 O3/UV PROCESS................................................................................. ............................................13

1.3.2 O3/H2O2 PROCESS...................................................................................................... ....................14

1.3.3 H2O2/UV PROCESS................................................................................. .......................................14

1.3.4 OTHER PROCESSES…………………….....................................................................................14

1.3.5 APPLICATIONS……………………………………….…............................................................14

1.4 DEFINITION OF PHOTO CATALYSIS..............................................................................................15

1.5 INTRODUCTION TO HETEROGENEOUS PHOTO CATALYSIS……………………..….……15-16

CHAPTER 2............................................................................... .............................................................17-25

2. LITERATURE REVIEW...................................................................................................................17-25

2.1 INTRODUCTION OF VARIOUS PROCESSES……………………………………………….…...17-18

2.2 STUDY OF VARIOUS PHOTO REACTORS…………………….…………………………..……18-23

2.3 DESIGNING OF PHOTO REACTOR…………………………………………….…………..…….23-24

2.4 LITERATURE REVIEW FOR MALACHITE GREEN……………………………………....…….24-25

CHAPTER 3...................................................................................................................................................26

3. SAMPLE SELECTION AND DESIGNING OF PHOTO REACTOR................................................26

CHAPTER 4…………………………………………………………………………………………..…….27

4. CHEMICALS AND APPARATUS USED……………………………………………………….…….27

CHAPTER 5……………………………………………………………………………………………..28-29

5. SYNTHESIS OF MALACHITE GREEN AND EXPERIMENT………………………………….28-29

CHAPTER 6……………………………………………………………………………………...………30-35

6. RESULTS AND DISCUSSION………………………………………………………………………30-35

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6.1 PRELIMINARY STUDIES…………………………………………………………………….…………..30

6.2 SAMPLE SCANNING…………………………………………………………………………….………..30

6.3 STANDARD CURVE………………………………………………………………………………...….30-31

6.4 ADSORPTION STUDY…………………………………………………………………………………31-35

CHAPTER 7.........................................................................................................................................................36

7. CONCLUSION................................................................................................................................................36

CHAPTER 8.........................................................................................................................................................37

8. REFERENCES................................................................................................................................................37

CHAPTER 9...................................................................................................................................................38-39

9. DESIGN ENGINEERING CANVAS......................................................................................................38-39

CHAPTER 10…………………………………………………………………………………………………..40

10. BUSINESS MODEL CANVAS……………………………………………………………………………40

CHAPTER 11......................................................................................................................................................41

11. PLAGIARISM REPORT.............................................................................................................................41

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LIST OF TABLES

Table-1: Comparison of oxidizing potential of various oxidizing agents……........................13

Table-2: Used chemicals with its purpose……........................................................................27

Table-3: Used apparatus and glasswares with its purpose……...............................................27

Table-4: Preliminary Studies………………………………………………….......................30

Table-5: Standard Curve Result……………………………………………….......................30

Table-6: Result of effect of TiO2 dosage without photo-degradation…..…….......................31

Table-7: Result of effect of TiO2 dosage with photo-degradation……....……......................32

Table-8: Effect of pH= 3 before and after UV treatment……………………........................33

Table-9: Effect of pH= 4 before and after UV treatment…………………..…......................33

Table-10: Effect of pH= 5 before and after UV treatment……………….…….....................33


Table-12: Effect of pH= 7 before and after UV treatment……….…………….....................34


Table-14: Effect of pH= 9 before and after UV treatment………………..…….....................34

Table-15: Effect of pH= 10 before and after UV treatment……………….……....................34

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LIST OF FIGURES

Figure-1: Classification of AOPs…………………………………………….........................13

Figure-2: Fixed bed photo catalytic reactor and its experimental setup………......................15

Figure-3: Continuous slurry photo reactor…………………………………….......................19

Figure-4: Schematic diagram of photo reactor………………………………........................20

Figure-5: Schematic diagram of a batch fixed photo reactor………………….......................21

Figure-6: Schematic diagram and photograph ……………….……….….….........................21

Figure-7: Experimental set up for Photo catalytic degradation……………….......................22

Figure-8: Schematic diagram of experimental set up………………………….......................23

Figure-9: Photo reactor at lab level during photo catalytic treatment…….….........................24

Figure-10: Outer view of photo reactor……………………………………............................24

Figure-11: Designed Photo Reactor Vessel…………………………….………………….....26

Figure-12: Schematic diagram of experimental setup…………….…….……………........…29

Figure-13: Standard Curve………………………………….…….….………………….…...31

Figure-14: Effect of TiO2 dosage without photo-degradation..………….………………..…32

Figure-15: Effect of TiO2 dosage with photo-degradation…..…………...…………….……32

Figure-16: Effect of pH after UV treatment on % degradation…………………..…….……35

Figure-17: AEIOU Summary…………………………..…….………………………………38

Figure-18: Empathy Summary……………………………………….………………………38

Figure-19: Ideation Canvas…………………………………………………..………………39

Figure-20: Product Development Canvas……………………………………………………39

Figure-21: Business Model Canvas……………………………………………….…….……40

ACRONYMS

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BOD BIOCHEMICAL OXYGEN DEMAND TCE TRICHLOROEHTYLENE COD CHEMICAL OXYGEN DEMAND

OD OPTICAL DENSITY SS STAINLESS STEEL FR FLOW RATE RPM REVOLUTION PER MINUTE m-DNB m-DINITROBENZENE PB PROCION BLUE NB NITROBENZENE UV-Vis ULTRAVIOLET-VISIBLE FT-IR FOURIER TRANSFORM-INFRARED TEM TRANSMISSION ELECTRON MICROSCOPY RY84 REACTIVE YELLOW 84 BB41 BASIC BLUE 41 ACF ACTIVATED CARBON FIBRE CPC CONCENTRATING PARABOLIC COLLECTOR BET BRUNAUER–EMMETT–TELLER XRD X-RAY DIFFRACTION EDS ELECTRONIC DATA SYSTEM SEM SCANNING ELECTRON MICROSCOPY LP LOW PRESSURE MP MEDIUM PRESSURE US ULTRASOUND EOP ELECTROCHEMICAL OXIDATION POTENTIAL PCD PHOTO CATALYTIC DEGRADATION AOPs ADVANCED OXIDATION PROCESSES MG MALACHITE GREEN UV ULTRA VIOLET TOC TOTAL ORGANIC CARBON PCE PERCHLOROETHYLENE

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CHAPTER 1

INTRODUCTION

1.1 INTRODUCTION OF ADVANCED OXIDATION PROCESS Advanced oxidation processes (AOPs) are used to oxidize complex organic constituents

found in waste water that are difficult to degrade biologically into simpler end products.

When chemical oxidation is used, it may not be necessary to oxidize completely a given

compound or group of compounds. In many cases, partial oxidation is sufficient to render

specific compounds more amenable to subsequent biological treatment or to reduce their

toxicity. The oxidation of specific compounds may be characterized by the extent of

degradation of the final oxidation products as follows:

a) Primary degradation: A structural change in the parent compound

b) Acceptable degradation (defusing): A structural change in the parent compound to the

extent that toxicity is reduced.

c) Ultimate degradation (mineralization): Conversion of organic carbon to inorganic

CO2

d) Unacceptable degradation (fusing): A structural change in the parent compound

resulting in increased toxicity

1.2 THEORY OF ADVANCED OXIDATION PROCESS

AOPs typically involve the generation and use of the hydroxyl free radical (OH.) as a strong

oxidant to destroy compounds that cannot be oxidized by conventional oxidants such as

oxygen, ozone, and chlorine. The relative oxidizing power of the hydroxyl radical, along with

other common oxidants, is summarized in Table-1. As shown, with the exception of fluorine,

the hydroxyl radical is one of the most active oxidants known. The hydroxyl radical reacts

with the dissolved constituents, initiating a series of oxidation reactions until the constituents

are completely mineralized. Non selective in their mode of attack and able to operate at

normal temperature and pressures, hydroxyl radicals are capable of oxidizing almost all

reduced materials present without restriction to specific classes or groups of compounds, as

compared to other oxidants.

AOPs differ from the other treatment processes (such as ion exchange or stripping) because

waste water compounds are degraded rather than concentrated or transferred into a different

phase. Because secondary waste materials are not generated, there is no need to dispose of or

regenerate materials.

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Oxidizing Agent Electrochemical Oxidation

Potential (EOP), V

EOP relative to Chlorine

Fluorine 3.06 2.25

Hydroxyl radical 2.80 2.05

Oxygen (Atomic) 2.42 1.78

Ozone 2.08 1.52

Hydrogen Peroxide 1.78 1.30

Hypochlorite 1.49 1.10

Chlorine 1.36 1.00

Chlorine Dioxide 1.27 0.93

Oxygen (Molecular) 1.23 0.90

Table-1: Comparison of oxidizing potential of various oxidizing agents

1.3 CLASSIFICATION OF ADVANCED OXIDATION PROCESSES

At the present time, a variety of technologies are available to produce OH. in the aqueous

phase. The various technologies are summarized in Figure-1. Of the technologies reported in

Table-2, only ozone/UV, ozone/hydrogen peroxide, ozone/UV/hydrogen peroxide, and

hydrogen peroxide/UV are being used on a commercial scale.

Figure-1: Classification of AOPs

1.3.1 O3/UV PROCESS

Production of the free hydroxyl radical with UV light can be illustrated by the following

reactions for the photolysis of ozone:

O3 + UV (λ<310 nm) O2 + O (1D)

O (1D) + H2O OH. + OH. (in wet air)

O (1D) + H2O OH. + OH. H2O2 (in water)

Where, O3 = ozone, UV = Ultraviolet Radiation, O2 = Oxygen

O (1D) = Excited oxygen atom. The symbol (1D) is a spectroscopic notation used to specify

the atomic and molecular configuration (also known as singlet oxygen)

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OH. = Hydroxyl radical. The dot (.) that appears next to the hydroxyl and other radicals is

used to donate the fact that these species have an unpaired electron.

The ozone/UV process is more effective when the compounds of interest can be degraded

through the absorption of the UV irradiation as well as through the reaction with the hydroxyl

radicals.

1.3.2 O3/H2O2 PROCESS

For compounds that do not adsorb UV, AOPs involving ozone/H2O2 may be more effective.

Compounds in water such as trichloroethylene (TCE) and perchloroethylene (PCE) have been

reduced significantly with AOPs using hydrogen peroxide and ozone to generate OH.. The

overall reaction for the production of hydroxyl radicals using hydrogen peroxide and ozone is

as follows:

H2O2 + 2O3 OH. + OH. + 3O2

1.3.3 H2O2/UV PROCESS

Hydroxyl radicals are also formed when water containing H2O2 is exposed to UV light (200

to 280 nm). The following reaction can be used to describe the photolysis of H2O2:

H2O2 + UV (λ = 200-280 nm) OH. + OH.

In some cases the use of the hydrogen peroxide/UV process has not been feasible because

H2O2 has a small molar extinction coefficient, requiring high concentrations of H2O2 and not

using the UV energy efficiently.

1.3.4 OTHER PROCESSES

Other reactions that yield OH. include the reactions of H2O2 such as TiO2 suspended in water,

which acts as a catalyst. Still others are currently under development.

1.3.5 APPLICATIONS

Based on numerous studies, it has been found that combined AOPs are more effective than

any of the individual agents (e.g., ozone, UV, hydrogen peroxide). AOPs are usually applied

to low COD waste waters because of the cost of ozone and/or H2O2 required generating the

hydroxyl radicals. Material that was previously resistant to degradation may be transformed

into compounds that will require further biological treatment.

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1.4 DEFINITION OF PHOTO CATALYSIS

Photo catalysis is a photochemical reaction induced by photon–absorption of a solid material,

a "photo catalyst” that remains unchanged during the reaction. Photo catalysis has a wide

variety of applications, e.g., degrading contaminants in aqueous solutions.

In a photo catalytic reaction, the absorbed photons excite the electrons in photo catalyst

particles, generating electron–hole pairs. The electron–hole pairs then initiate a set of red-ox

reactions, or recombine to lose the absorbed energy to heat.

In such reactors concentrations are independent of location; the light distribution may still be

inhomogeneous. As the light travels through the photo reactor, it is scattered and absorbed by

the photo catalyst particles and its intensity drops; Since photons initiate the photoreaction,

this results in a non–uniform reaction rate in the photo reactor. Fixed bed photo catalytic

reactor and its experimental setup are shown in figure-2.

Figure-2: Fixed bed photo catalytic reactor and its experimental setup

1.5 INTRODUCTION TO HETEROGENEOUS PHOTO CATALYSIS

It uses catalysts to carry out the degradation of compounds and separates the product with

greater ease. Catalyst characteristics are high activity, resistance to poisoning and long term

stability at high temperature, mechanical stability and resistance to attrition, non-selectivity in

most cases and physical and chemical stability under a wide range of conditions. Catalysts

can be classified as: (a) Metal catalysts (b) Metal oxide catalysts (c) Organo-metal catalysts.

The process involves illumination of an aqueous suspension of a semiconductor. The light

energy generates photo electron hole pairs which can migrate to the interface where they

react with adsorbed redox species. The process can be represented as:

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TiO₂ + hʋ TiO₂(e⁻ + h⁺)

TiO₂(h⁺) + H₂O TiO₂ + H⁺ + OH·

TiO₂ (h⁺) + OH⁻ TiO₂ + OH·

TiO₂(e⁻) + O₂ TiO₂ + O₂·⁻

O₂·⁻ + H⁺ HO₂·

Dye + OH· degradation products

Dye + h⁺ oxidation products

Dye + e⁻ reduction products

The degradation of dyes depends on several parameters such as pH, catalytic conc., substrate

concentration and the presence of electron acceptors. Benefits of AOPs are described below:

(i) Effective in removing resistant organic compounds

(ii) Capable of complete mineralization of organic compounds to CO2.

(iii)Not susceptible to the presence of toxic chemicals

(iv) Generally produce innocuous end products

(v) Can be used to pre-treat toxic compounds so that they can be bio-treated

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CHAPTER 2

LITERATURE REVIEW

2.1 INTRODUCTION OF VARIOUS PROCESSES

Adel al-kdasi et al. gave an overview of basis and treatment efficiency for different AOPs.

There are mainly 4 processes are described for the degradation of various textile effluent

contamination. Those methods are: O3/UV, O3/H2O2, O3/H2O2/UV, and H2O2/UV. In this,

Adel al-kdasi et al. suggested that AOPs are powerful treatment processes for refractory

compounds in textile effluent. There are many research needs to be done in the field of AOPs

to study operation sequence, efficiency under different controlled condition.

J. M. Poyatos et al. gave classification of all Advanced Oxidation Processes and describes its

reactions, and application to treatment of effluent with complex organic constituents. There

are mainly all techniques of AOP are described, but we focus on only 5 main techniques that

are: (i) O3/UV (ii) H2O2/UV (iii) O3/H2O2/UV (iv) Photo-Fenton Process (v) Heterogeneous

Photo catalysis. In O3/UV Process, UV light is used for the photolysis of O3 at 253.7nm

wavelength which generates more OH•. Reaction mechanism of this process is given below:

H2O + O3 +UV 2OH•+O2

2OH• H2O2

O3/UV Process has advantages like: (a) Supplemental disinfectant, (b) More efficient than O3

alone, and (c) No toxic compounds formed. Disadvantage of this method is: (a) Sometimes

UV light is absorbed by organic molecule instead of photolysis of O3 which decreases

efficiency. In H2O2/UV Process, UV light of 200-280nm used which helps in cleavage of O-

O bond.MP-UV & LP-UV used. Reaction mechanism of this process is given below:

H2O2+UV 2OH•

H2O2+OH•OH2

•+H2O

H2O2+OH2•OH•+O2+H2O

2OH2•H2O2+O2

2OH•H2O2

H2O2/UV Process has advantages like: (a) O2 is formed during the process hence it can be

utilized for aerobic biological decay process, (b) Not dependent on PH, (c) Supplemental

disinfectant, and (d) Can be carried out under ambient conditions. Disadvantages of this

method are: (a) solar light can’t be used, (b) H2O2 have poor absorption characteristics hence

H2O absorb max. UV light, (c) Need of special reactors, and (d) Stoichiometrically less

efficient in generating OH• as compared to O3/UV. In O3/H2O2/UV Process, H2O2 is used in

O3/UV process. It is combination of O3/UV and O3/H2O2.

2O3+H2O2+UV2OH•+3O2

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Advantages of this process are: (a) Increases generation of OH• and accelerates

decomposition of O3, and (b) Gives COD and TOC removal efficiency of >90%.

Disadvantage of this process is: (a) Most expensive. Photo-Fenton process uses UV light

which helps in photolysis of Fe3+ complexes formed in above process to regenerate Fe2+.

Overall reactions are given below:

Fe+2+H2O2Fe+3+OH-+OH•

Fe+3+H2O+UVFe+2+H++OH•

H2O2+hv 2OH•

Advantages of this method are: (a) Less formation of sludge, (b) Used to remove recalcitrant

compounds, (c) Small size of reactor, and (d) High degradation velocity. Disadvantages of

this method are: (a) pH adjustment, (b) UV light increases cost, and (c) Sludge treatment.

Heterogeneous Photo catalysis includes use of semiconductor which acts as a catalyst and a

source of light to excite electrons from valence band to conduction band. So, holes and

electrons are generated. Reactions mechanism is given below:

TiO2+UVTiO2 (e - + h+)

TiO2h+ + OH-

adTiO2+ OH•

H2O2 + e-OH•+ OH-

Advantages of this method are: (a) Very highly efficient, (b) Complete consumption of H2O2

and led to non-toxic residue, and (c) Can be performed at higher wavelengths (300-380 nm)

as compared to other UV oxidation processes. Disadvantages of this method are: (a) Photo

catalysts are not readily available, (b) Energy transfer problem, and (c) Increase in

concentration of H2O2 leads to decrease in adsorption. Figure-2 shows the conclusion and

described techniques in this revision.

2.2 STUDY OF VARIOUS PHOTO REACTORS

Sanjay P Kamble et al. described the degradation of 1, 3-dinitrobenzene (m-DNB). In this

work, the degradation rate and efficiency are compared of nitrobenzene and 1, 3-

dinitrobenzene under artificial UV radiation. It was found that a variety of phenolic

intermediates are formed via hydroxyl radicals attacking the parent compound. The effect of

the various operational parameters on the PCD of m-DNB was studied. Continuous

experiments were carried out in a stainless-steel slurry bubble column reactor of 0.2m

(internal diameter) ×1.2m length and capacity 30 L, utilizing artificial UV radiation. A

schematic of the slurry bubble column reactor is shown in Figure-3. A Philips low-pressure

125W UV tube (1.0m length, 0.0254m (outer diameter) and λ = 254 nm) was placed inside a

quartz tube for its isolation from the reaction mixture. An aqueous solution of m-DNB was

prepared in tap water in a 175 L agitated tank. A metering pump was used for delivering m-

DNB solutions to the top of the stainless-steel column, and an oil-free air compressor was

used to sparge the air at the bottom of the column through a sintered stainless-steel disk. Air

was bubbled at sufficiently high velocity to keep all the TiO2 in suspension. Experiments

were performed for 7 hours. The adsorption of m-DNB on the surface of the catalyst is

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critical, and depends on the pH of the solution and on the concentration and type of anions

present. The PCD rate of m- DNB at its self-pH is higher than that under alkaline or acidic

pH conditions. It was observed that the rate of PCD of m-DNB is relatively low compared

with that of nitrobenzene and the reason for this behaviour is the poor adsorption of m-DNB

compared with NB.

Figure-3: Continuous slurry photo reactor

Juan M. Coronado et al. described the effect of reactor configuration and catalyst’s

characteristics on PCD of TCE vapours under sunlight. In this revision, two types of

continuous flow reactors namely (i) a compound parabolic collector (CPC) and (ii) a simple

flat reactor. Three different photo catalysts based on TiO2 were utilized: (i) commercial

powders calcined at 500°C (ii) a TiO2-xNx sample synthesized by treating the commercial

sample at 500°C in an NH3 gas flow, and (iii) TiO2 thin film coatings on differently shaped

borosilicate glass supports prepared by a sol-gel procedure. The commercial TiO2 sample

gives the highest efficiency while TiO2-xNx sample shows somewhat less efficiency and sol-

gel TiO2 sample shows the highest TCE degradation rate per mass of catalyst. For high

volume of effluent and high concentration of TCE, CPC is advantageous. A reactor consists

of two CPCs with two Pyrex glass tubes length of 160 cm, external diameter of 32 mm, and

internal diameter of 29 mm placed on the focal line. Both CPCs were mounted on fixed

platform tilted 40 degree local latitude and oriented south. Figure-4 displays a scheme of the

setup used for photo catalytic activity measurements, showing a sketch of the flat reactor.

Removal of TCE using solar irradiation can be efficiently achieved using one-sun photo

reactors. Differences in the efficiency of PCD between flat and CPC reactors are relatively

small.

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Figure-4: Schematic diagram of photo reactor

FU Ping-feng et al. gave an idea about a batch fixed bed photo reactor, using activated carbon

fibres (ACF) supported TiO2 photo catalyst (TiO2/ACF), to carry out photo catalytic

degradation of Methylene blue (MB) solution. The effects of TiO2 particle size, loaded TiO2

amount, initial MB concentration, airflow rate and successive run on the decomposition rate

were investigated. The photo catalytic efficiency still remained nearly 90% after 12

successive runs, showing that successive usage of the designed photo reactor was possible.

The schematic diagram of a batch fixed bed photo reactor is shown in Figure-5. The prepared

TiO2/ACF photo catalyst was fixed on the internal surface of a cuboid Aluminium mesh

(L×W×H=60 mm×60 mm×300 mm) to produce a catalyst unit. A cuboid reaction cell

(L×W×H=310 mm×64 mm×310 mm) was separated into 5 small cells, into which five

cuboid catalyst units were installed. A 24 W low pressure mercury lamp was inserted along

the axis of each catalyst unit. Air was bubbled into reaction solution from 5 air distributors to

stir the aqueous solution, ensuring a constant concentration of dissolved oxygen. The results

show that the smaller the TiO2 particle size is, the higher degradation rate achieves. The

degradation rate significantly increases with the reduced initial MB concentration. The photo

catalytic efficiency of the fixed bed photo reactor has slightly reduced about 10% after 12

successive runs. Under weak UV illumination, Methylene Blue (MB) can be rapidly

degraded.

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Figure-5: Schematic diagram of a batch fixed photo reactor

Noureddine Barka et al. described the photo catalytic degradation of an azo reactive dye,

Reactive Yellow 84 (RY84), in aqueous solutions using TiO2 coated non-woven paper. In

this revision, effects of various operational parameters on PCD are shown. The experimental

results show that adsorption is an important parameter controlling the apparent kinetics

constant of degradation. The degradation increases with increase in by temperature and in

acidic pH range. Figure-6 shows a cylindrical batch reactor opened at air with 8 cm in

diameter and 12 cm in working height. The water jacket with a diameter of 5 cm is used for

cooling. The photo reactor was recovered inside with (11 x 25 cm) of the photo catalyst. A

high pressure 125 W Philips UV-lamp is used as light source and it is placed in axial position

inside the water jacket. The reactor was maintained in low continuous stirring (100 rpm) by

means of a magnetic stirrer. The experiments were carried out by loading 500 ml of the dye

solutions in the photo catalytic reactor. The results show that the maximum dye adsorption

and photo catalytic degradation was higher for pH <3.

Figure-6: Schematic diagram and photograph

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S. Mohammadi-Aghdam et al. described PCD of Basic Blue 41 (BB41) using TiO2 nano

composite films, immobilized on glass substrates using the sol–gel method, in a semi-batch

rectangular photo reactor (irradiated with a UV light). The coatings were characterized by X-

ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron

microscopy (SEM). Photo catalytic mineralization of BB41 was monitored by chemical

oxygen demand (COD) decrease, changes in UV–Vis spectra and FT-IR spectra. A

rectangular semi-batch flow Photo reactor (400mm x 150 mm x150 mm) consists of a high-

pressure mercury lamp (15 W) encircled by a quartz tube (outer diameter = 32 mm and inner

diameter =30 mm) at the centre of it. For measuring UV light intensity, the UV lamp was

centred in a quartz tube and the light intensity of 0.9 mW cm-2 was measured by a UV-Lux-

IR meter at the distance of 18 mm, which was equal to the distance between the outer surface

of the quartz tube and the inner surface of the Pyrex photo reactor. Photo reactor was covered

with the metallic protection to prevent from diffusion of the harmful UV irradiation to the

laboratory. The nano composite TiO2 films were placed in the inner wall of reactor. In each

set-up prior to irradiation, 1200 mL of BB41 solution with a desired initial concentration was

circulated over the catalyst by a water pump to obtain an adsorption–desorption equilibrium.

A liquid flow meter was used to adjust the FR. The reactor consisted of a digital heater

thermometer which was inserted into the feed tank to maintain the reaction temperature at a

constant value with accuracy of ±0.50C. The UV lamp and the pump were switched on at the

beginning of each experiment. Air was entered to the reaction system at the constant flow rate

using a micro-air pump. Sampling was carried out at regular time intervals during irradiation

and analyzed by a double beam UV–Vis spectrophotometer to measure the concentration of

the dye.

Figure-7: Experimental set up for Photo catalytic degradation

S.W. Yao et al. described photo catalysis process by SiO2/TiO2, which is prepared by sol-gel

method. They are characterized by SEM/EDS, XRD, and BET specific surface area

measurement. The as-prepared SiO2/TiO2 particles are used as the fluidizing media in a

fluidized bed photo reactor and toluene is degraded therein. The results show that the

contaminated stream containing toluene with the concentration as high as 1000 ppm can be

continuously degraded in the fluidized bed photo reactor. Efficiency of toluene removal is 30-

40% at steady state. The configuration of the photo catalytic degradation system is shown in

Figure-8. The quartz glass cylindrical reactor is 50 mm in internal diameter and 320 mm in

length. A 15 W UV lamp is mounted at the centre of the reactor. Air is introduced to the

system from a 7.5 kgW/m2 tank connected to a compressor and dehumidified in the dryer.

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The air flow rate is controlled by the gas flow controller and is controlled at 5 L/min. The

concentrations of toluene vapour and water vapour are controlled by toluene generator and

water evaporator, respectively. The toluene inlet concentration and outlet concentration are

measured by a gas chromatograph.

Figure-8: Schematic diagram of experimental set up

2.3 DESIGNING OF PHOTO REACTOR

Chhotu Ram described photo degradation of Procion Blue (PB) dye in specially designed

reaction vessel equipped with UV tubes and constant stirring of solution was ensured at

constant temperature. Experiments were performed in slurry mode in both UV and solar light

at optimized condition. Photo catalytic treatment of dye and effluent were performed in batch

experiments. The degradation of dye and textile effluent has been investigated in terms of

change in colour by measuring absorbance, reduction in COD and solid content. Various

process parameters like catalyst dose, pH, concentration of oxidant, initially pollutant

concentration were varied and their effects have been analyzed. For photo catalytic UV

reactor was used which was rectangular having dimensions of 4.5 feet length, 3 feet width

and 3.5 feet height and made up of iron. Roof of the reactor was made up of wooden; seven

UV tubes (36 Watt each) were attached with the roof. Temperature inside the reactor was

maintained by an exhaust fan. Four magnetic stirrers were fitted in the reactor to carry out the

photo catalytic reaction in slurry mode. Two different view of photo reactor are shown in

figure-9 and figure-10.

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Figure-9: Photo reactor at lab level during photo catalytic treatment

Figure-10: Outer view of photo reactor

2.4 LITERATURE REVIEW OF MALACHITE GREEN

S.Shanthi et al. found that the Co Precipitation technique has been used for the synthesis of

zinc oxide nano particle. The four samples obtained by the Co Precipitation technique were

characterized by FTIR, and SEM instrumental method. The size of nano particles decreased

with increase in irradiation time and power of the microwave radiation. The photo catalytic

degradation of dye was carried out using different sources of energy like solar radiation,

microwave radiation and ultra sound radiation. Among the three different energy sources the

sono chemical degradation treatment is found to be more effective than solar radiation and

microwave radiation treatment with respect to time and initial concentration. The photo

catalytic degradation of malachite green dye obeyed pseudo first order kinetics. The photo-

catalytic degradation of dyes can be carried out with all the three sources of radiations, and

the reaction can proceed to complete degradation. So, this technique can be used for the

treatment of industrial effluents containing dyes.

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Hiral Soni et al. did photo-catalytic study in series of flasks containing dye and nano

particles. The effect of dose of catalyst on various concentration of dye solution was

investigated. Isotherms were run by taking selected different concentrations of malachite

green and determined using a UV-visible spectrometer. Catalysts containing tubes were

placed on UV- radiation lamp. Four 15 W low pressure mercury UV tubes emitting near UV

radiation with a peak at 365 nm were used. The residual dye concentration in each solution

was measured spectrophotometrically at the corresponding λmax. Dye containing tube without

nano particles was also placed on UV to show that though during UV irradiation, direct

photolysis of dyes could occur, mineralization of dyes only takes place in the presence of a

photo-catalyst and the extent of removal of the dye, in terms of the values of percentage

removal has been calculated. The ultraviolet (UV) light irradiation of the dye by using nano

particles of TiO2 as a catalyst has yielded absolute decolouration for a catalyst loading of

20mg. Molecular formula of Malachite Green is C23H25ClN2 and chemical structure of

Malachite Green is given below:

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CHAPTER 3

SAMPLE SELECTION AND

DESIGNING OF PHOTO REACTOR

After reading above discussed literatures, Malachite Green dye was selected as our sample.

For the degradation of above sample dye Heterogeneous Photo-catalysis process was used

with Titanium Dioxide solid catalyst.

Designed photo reactor made up of glass sheets. Dimensions of photo reactor are given

below:

a) Length = 6 inches

b) Width = 20 inches

c) Height = 12 inches

Two UV tubes were used of 8 inches with 11 watts each. Three motors were installed of 200

RPM each on both corner and it provides stirring, which is connected with battery. Cooling

effect is provided by circulating cooling water around the reactor. This reactor design is

mainly used for batch process but it can be used for continuous process also.

Figure-11: Designed Photo-reactor Vessel

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CHAPTER 4

CHEMICALS AND APPARATUS USED

Chemicals Used Purpose

HCl (Hydrochloric Acid) (98% strong) To adjust pH and in synthesis of Malachite

Green dye

NaOH (Sodium Hydroxide) (98% strong) To adjust pH

TiO2 (Titanium Dioxide) As a solid catalyst for photo-degradation

Copper Turning In synthesis of MG dye

HNO3 (Nitric Acid) (95% strong) In synthesis of MG dye

Ammonia In synthesis of MG dye

NaHCO3 (Sodium Bicarbonate) In synthesis of MG dye

K2Cr2O7 (Potassium Dichromate) (0.25N) For measuring COD

H2SO4 (Sulphuric Acid) (96%strong) For measuring COD

HgSO4 (Mercuric Sulphate) For measuring COD

Ferrous Ammonium Sulphate (0.1 N) For titration in measuring COD

Ferroin Indicator As an indicator in measuring COD

Table-2: Used chemicals with its purpose

Apparatus and Glasswares Used Purpose

Weighing Machine To weigh the powder of TiO2 and NaHCO3

Magnetic Stirrer with Bid For stirring the solution during synthesis of

dye and UV-treatment

Filter Paper To filter out precipitates

Laminar Air Flow For applying UV-treatment

UV-Visible Spectrophotometer (Double

Beam)

To check absorbance

Beakers For making different solutions and storing

mixtures

Conical Flask For titration and storage of solutions

Funnel For pouring the solutions into burette

Pipette To pipette out chemicals

Burette For titration

Measuring Cylinder To measure accurate volume of solutions

Rotary Flask Shaker For shaking or mixing of chemicals

Cuvette To keep sample in spectrophotometer

Table-3: Used apparatus and glasswares with its purpose

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CHAPTER 5

SYNTHESIS OF MALACHITE GREEN AND EXPERIMENT

SYNTHESIS OF MALACHITE GREEN

Malachite Green (MG) was prepared dye in laboratory. Procedure for synthesizing MG is

described below:

Take Copper Turning of about 3-5 grams. Add nitric acid into it until copper is fully

dissolved in it. It gives dark green colour to the solution.

Stir the mixture for 10-15 minutes. Then add ammonia solution give it a blue colour.

Take another beaker and prepare carbonic acid into it. For that, take sodium

bicarbonate powder of about 3 grams. Add hydrochloric acid into it until powder of

sodium bicarbonate is fully dissolved.

Then filter out the above solution to get carbonic acid and filter the precipitates of

sodium chloride.

Take filtrate of carbonic acid and add it into blue colour solution. It gives green colour

to the mixture and hence MG dye is prepared in aqueous form.

EXPERIMENT

200 ml of MG dye was prepared and add 800 ml distilled water into it to make the

volume of 1000 ml and hence we get 200 ppm concentration of synthesized dye.

Measure the natural pH of synthesized MG dye and it is 1.6. We scanned 200 ppm

solution into UV-Visible spectrophotometer and found optimum wavelength as 323

nm.

Make different concentration out of original dye sample of 200 ppm concentration by

diluting it like 100 ppm, 50 ppm, 25 ppm, 12.5 ppm and take its absorbance at 323 nm

wavelength and make standard curve from it.

Then measure initial COD of the sample and it is 720 mg/L.

Take five beakers each of 100 ml sample of natural pH and of 200 ppm concentration.

Then add different dosages of TiO2 like 0.1 gm, 0.2 gm, 0.3 gm, 0.4 gm, 0.5 gm

respectively in each beaker.

Give mixing of 30-45 minutes to each of five samples without UV light. Then take

absorbance of these five samples at 323 nm wavelength.

Give UV-treatment to each of five samples for 1 hour by keeping it in laminar air

flow and measure absorbance of each at optimum wavelength.

Maximum degradation is at 0.2 gm dosage of TiO2. Then measure its final COD as

600 mg/L.

Change its original pH to 3, 4, 5, 6, 7, 8, 9, and 10 and keep dosage of 0.2 gm TiO2 in

each sample. Give just mixing of 30-45 minutes and then take absorbance at 323 nm

wavelength.

Give UV illumination to each different sample for 1 hour and measure its absorbance

at optimum wavelength.

Prepare MG dye of five litres and give similar treatment processes as mentioned

above and 83-84% of degradation was achieved. Schematic diagram of our

experimental setup is shown below:

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Figure-12: Schematic diagram of experimental setup

In above Figure, nomenclatures denote:

1- Battery

2- Glass photo-reactor

3- UV tubes

4- Wiring

5- Motor with paddles

6- Wood Cover

1

2

3

4

5

6

30 | P a g e

CHAPTER 6

RESULTS AND DISCUSSION

6.1 PRELIMINARY STUDIES

Technical grade dye namely Malachite Green (MG) was used as sample for heterogeneous

photo-catalysis.

Parameters Result

pH 1.6

COD 720 mg/L

Optimum Wavelength (λmax) 323 nm

Absorbance 2.276

Initial Concentration 200 ppm

Table-4: Preliminary Studies

6.2 SAMPLE SCANNING

Scanning of the sample was done in the wavelength range of 200 to 1000 nm and we got

optimum wavelength as 323 nm.

6.3 STANDARD CURVE

MG was used of 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm concentration to get standard

curve and measured its absorbance at optimum wavelength i.e. 323 nm. Results are given

below:

Absorbance Concentration (ppm)

0 0

0.213 12.5

0.416 25

0.653 50

1.249 100

2.276 200

Table-5: Standard Curve Result

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Figure-13: Standard Curve

6.4 ADSORPTION STUDY

TiO2 was used as a solid semi-conductor metal oxide catalyst for adsorption. Sample dye MG

was treated with and without photo-degradation effect.

DARK STUDY

(i) Effect of TiO2 dosage without photo-degradation

To study the effect of variation of dose of photo catalyst, the initial concentration of the dyes

and initial pH were kept constant and the dose of photo catalyst was varied. Minimum

amount of photo catalyst required for the maximum removal of dye was determined. Results

for finding optimum dose on natural pH of sample are given below:

pH= 1.6, mixing time= 30 min., Concentration= 200 ppm, volume of sample= 100 ml,

wavelength= 323 nm, Before UV treatment

Dose of TiO2 Absorbance Final Concentration % degradation

0.1 gm 0.964 81.690324 59.154838

0.2 gm 0.853 72.284073 63.8579635

0.3 gm 0.884 74.911044 62.544478

0.4 gm 1.061 89.910201 55.0448995

0.5 gm 1.059 89.740719 55.1296405

Table-6: Result of effect of TiO2 dosage without photo-degradation

Following formula was used for finding percentage degradation:

Percentage Removal (%R) = 100*(Ci-Cf)/Cf,

Where, Ci= initial concentration of dye (ppm); Cf = final concentration of dye (ppm) at given

time.

y = 0.0117xR² = 0.9902

0

0.5

1

1.5

2

2.5

0 50 100 150 200 250

Ab

sorb

ance

Concentration (ppm)

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Figure-14: Effect of TiO2 dosage without photo-degradation

PHOTO-CATALYTIC DEGRADATION

(i) Effect of TiO2 dosage with photo-degradation

UV illumination was given to the sample which is degraded only under the effect of TiO2

dosage.

After UV treatment of 1 hr with stirring


0.1 gm 0.527 44.658507 77.6707465

0.2 gm 0.394 33.387954 83.306023

0.3 gm 0.495 41.946795 79.0266025

0.4 gm 0.576 48.810816 75.594592

0.5 gm 0.731 61.945671 69.0271645

Table-7: Result of effect of TiO2 dosage with photo-degradation

Figure-15: Effect of TiO2 dosage with photo-degradation

54

55

56

57

58

59

60

61

62

63

64

65

0 1 2 3 4 5 6

% D

egra

da

tio

n

Concentration of TiO2 (mg/L)

0

10

20

30

40

50

60

70

80

90

0 1 2 3 4 5 6

% D

egra

da

tio

n

Concentration of TiO2

33 | P a g e

(ii) Effect of pH

The effect of variation of pH of dye solution on the photo degradation reaction was

determined by keeping the initial concentration and dose as the optimum values in all

experiments and varying pH. It is established that surface properties of semiconductor are

responsible for photo-catalytic process. The effect of pH was studied after fixing the dose of

0.2 gm of TiO2. pH was changed in the range between 3 to10.

pH= 3, mixing time= 30 min., Concentration= 200 ppm, volume of sample= 100 ml,

wavelength= 323 nm



0.2 gm 0.887 75.165267 62.4173665

Table-8: Effect of pH= 3 before and after UV treatment


wavelength= 323 nm



0.2 gm 0.906 76.775346 61.612327



wavelength= 323 nm



0.2 gm 0.972 82.368252 58.815874



wavelength= 323 nm



0.2 gm 1.263 107.027883 46.4860585


34 | P a g e


wavelength= 323 nm



0.2 gm 1.438 121.857558 39.071221


So, we conclude from above results of acidic pH that under acidic condition, the degradation

of MG gives better result and we got maximum degradation on natural pH i.e. 83-84% of

degradation.


wavelength= 323 nm



0.2 gm 1.875 158.889375 20.5553125



wavelength= 323 nm



0.2 gm 2.071 175.498611 12.2506945



wavelength= 323 nm



0.2 gm 2.193 185.837013 7.0814935


So, we conclude from above results of alkaline pH that under alkaline condition, the

degradation of MG gives less degradation efficiencies due to the formation of intermediates

at basic condition.

35 | P a g e

Figure-16: Effect of pH after UV-treatment on % degradation

Maximum degradation was achieved on its natural pH 1.6 and it is 83-84%.

0

10

20

30

40

50

60

70

80

90

0 2 4 6 8 10 12

% d

egra

da

tio

n

pH

36 | P a g e

CHAPTER 7

CONCLUSION

Heterogeneous photo catalysis is an emergent process for the degradation of refractory

organic substances in wastewater. It is the superior technique than conventional treatment

methods to reduce the organic load in wastewater. This process requires reactor, catalyst and

source of light with continuous stirring for adsorption and degradation of refractory

substances. To achieve these requirements, we have designed a photo reactor.

The photo reactor has been made from glass with dimensions 6’’ x 20’’ x 12’’ (L x W x H).

We have used two UV tubes of 11W each, for source of light which is of 8” each. The three

motors of 200 RPM each were mounted on shaft which will be rotating, thus helping in

stirring the solution. Cooling was provided by circulating cooling water because UV tubes

generate high energy which will produce heat.

MG dye was taken as a sample and carried out series of experiments. Firstly, experiment was

done on its natural pH that is 1.6 and varying dosage of TiO2 and maximum degradation was

achieved on 0.2 gm of TiO2 dosage. Then UV illumination was applied. Then this experiment

was carried out at different pH and optimized dosage of TiO2. Maximum degradation of 83-

84% was achieved at optimized dosage of TiO2 and optimum pH. It gives best result on its

natural pH. Under acidic condition, it gives better result and degradation of MG dye takes

place but under basic condition, intermediates may be formed and thus it doesn’t give

positive results. So, finally it is decided to work on natural pH, 200 ppm concentration and

five litres of sample volume with 10 gm of TiO2 dosage. Initial and final COD of sample

were measured and it is 720 mg/L and 600 mg/L respectively. Colour removal can be also

seen visually.

37 | P a g e

CHAPTER 8

REFERENCES

1. J. M. Poyatos, M. M. Muñio, M. C. Almecija, J. C. Torres, E. Hontoria, F. Osorio,

Advanced Oxidation Processes for Wastewater Treatment: State of the Art Water Air Soil

Pollution, 205,187–204,2010.

2. Adel al-kdasi, azni idris, katayon saed, chuah teong guan, Treatment of Textile

Wastewater by Advanced Oxidation Processes – A Review, Global Nest ,6, 222-230,

2005

3. S.W. Yao and H.P. Kuo, Photo catalytic degradation of toluene on SiO2/TiO2 photo

catalyst in a fluidized bed reactor, Procedia Engineering, 102, 1254, 2015.

4. Juan M. Coronado, Benigno Sánchez, Fernando Fresno, Silvia Suárez, Raquel Portela,

Influence of Catalyst Properties and Reactor Configuration on the Photo catalytic

Degradation of Trichloroethylene under Sunlight Irradiation, Journal of Solar Energy

Engineering, 130, 4, 2008

5. FU Ping-feng, ZHAO Zhuo, PENG Peng, DAI Xue-gang, - Photo degradation of

Methylene Blue (MB) in a Batch Fixed Bed Photo reactor Using Activated Carbon Fibres

Supported TiO2 Photo catalyst, The Chinese Journal of Process Engineering, 8, 65-71,

2008

6. S. Mohammadi-Aghdam, R. Marandi, M.E. Olya, A.A. Mehrdad Sharif, Kinetic

modelling of BB41 photo catalytic treatment in a semi-batch flow photo reactor using a

nano composite film, Journal of Saudi Chemical Society, 29, 957-963, 2013

7. Noureddine Barka, Samir Qourzal, Ali Assabbane, Abderrahman Nounah, Yhya Ait-

Ichou, Photo catalytic degradation of an azo reactive dye, Reactive Yellow 84, in water

using an industrial titanium dioxide coated media, Arabian Journal of Chemistry, 3, 279-

283, 2010

8. Sanjay P Kamble, Sudhir B Sawant and Vishwas G Pangarkar, Photo catalytic

degradation of m-dinitrobenzene by illuminated TiO2 in a slurry photo reactor, Journal of

Chemical Technology and Biotechnology, 81, 365-373, 2005

9. Chhotu Ram, Thesis, Studies On The Photo catalytic Degradation Of Dye And Textile

Wastewater, 2008

10. S. Shanthi, R. Manjula, M. Vinulakshmi, R. Rathina Bala, Studies on the Photo

Degradation of Malachite Green Dye by the Synthesized ZnO Nano Particles with

different Sources of Energy, International Journal of Research in Pharmacy and

Chemistry, 4 (3), 571-576, 2014

11. Hiral Soni, Nirmal Kumar J. I., UV Light Induced Photocatalytic Degradation of

Malachite Green on TiO2 Nanoparticles, International Journal of Recent Research and

Review, Vol. VII, 10-15, 2014

38 | P a g e

CHAPTER 9

DESIGN ENGINEERING CANVAS

Figure-17: AEIOU Summary

Figure-18: Empathy Summary

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Figure-19: Ideation Canvas

Figure-20: Product Development Canvas

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CHAPTER 10

BUSINESS MODEL CANVAS

Figure-21: Business Model Canvas

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CHAPTER 11

PLAGIARISM REPORT

Hyperlink for our plagiarism report is given below:

Semester-7: https://www.thepensters.com/free-plagiarism-checker

report.html?id=4fe4e8488805247f91f06ee9ec84580e_1445056713:7035002

Semester-8:

https://www.thepensters.com/free-plagiarism-checker

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